CN117085738A - Dehydrogenation catalyst and preparation method and application thereof - Google Patents
Dehydrogenation catalyst and preparation method and application thereof Download PDFInfo
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- CN117085738A CN117085738A CN202311354642.7A CN202311354642A CN117085738A CN 117085738 A CN117085738 A CN 117085738A CN 202311354642 A CN202311354642 A CN 202311354642A CN 117085738 A CN117085738 A CN 117085738A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 109
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- -1 carboxylate ion Chemical class 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 14
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 12
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005903 acid hydrolysis reaction Methods 0.000 claims abstract description 6
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011232 storage material Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 17
- 101150003085 Pdcl gene Proteins 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- HOQAPVYOGBLGOC-UHFFFAOYSA-N 1-ethyl-9h-carbazole Chemical compound C12=CC=CC=C2NC2=C1C=CC=C2CC HOQAPVYOGBLGOC-UHFFFAOYSA-N 0.000 claims description 8
- 150000002825 nitriles Chemical class 0.000 claims description 7
- 229920000090 poly(aryl ether) Polymers 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- RDLZRCSOLOTEPK-UHFFFAOYSA-N 4-propoxybenzene-1,2-dicarbonitrile Chemical compound CCCOC1=CC=C(C#N)C(C#N)=C1 RDLZRCSOLOTEPK-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 239000002211 L-ascorbic acid Substances 0.000 claims description 3
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000000354 decomposition reaction Methods 0.000 abstract description 6
- 238000011068 loading method Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- DSISJSHTHDGGAG-UHFFFAOYSA-N 1-tetradecyl-9h-carbazole Chemical compound C12=CC=CC=C2NC2=C1C=CC=C2CCCCCCCCCCCCCC DSISJSHTHDGGAG-UHFFFAOYSA-N 0.000 abstract 1
- 239000000571 coke Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0015—Organic compounds; Solutions thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to the technical field of dehydrogenation catalysts, and discloses a dehydrogenation catalyst, a preparation method and application thereof. The dehydrogenation catalyst comprises: a carboxylate ion-containing carrier and an active component; the carrier containing carboxylate ions is obtained by acid hydrolysis of a carrier containing cyano groups, and the active component comprises at least one selected from VIII group elements. The carrier containing carboxylate ions in the dehydrogenation catalyst is obtained by acid hydrolysis of a carrier containing cyano groups, and the carrier containing carboxylate ions is coordinated and combined with an active component, so that the active component of the dehydrogenation catalyst has low loading capacity, high dispersity, good stability and small particle size; the preparation method simplifies the operation conditions and the process flow, and is convenient for industrial production; the catalyst is used for dehydrogenation of organic hydrogen storage materials such as laurylethyl carbazole, 18H-dibenzyl toluene, methylcyclohexane and naphthalene, can effectively improve dehydrogenation efficiency, reduces the raw material decomposition rate and is difficult to coke.
Description
Technical Field
The invention relates to the technical field of dehydrogenation catalysts, in particular to a dehydrogenation catalyst and a preparation method and application thereof.
Background
Energy is the basis of human society development, but the existing energy system has the defects of environmental pollution, low efficiency and the like. The hydrogen energy source is abundant, easy to obtain, low-carbon and sustainable, and compared with other hydrogen storage methods, the liquid organic hydrogen carrier has high hydrogen storage density and normal temperature and normal pressureThe lower stability is good, the safety is higher, and the storage and the transportation are relatively simple. At present, the ethylcarbazole (NEC) receives extensive attention, and meets the requirement of an on-vehicle hydrogen storage system in the United states>5.5wt%H 2 ) Is not limited. The hydride can release hydrogen at low temperature, and the 12H-NEC is liquid at normal temperature and normal pressure, so that the hydride can better match with the existing facilities. In addition, the organic liquid hydrogen storage is mainly divided into two units of hydrogenation and dehydrogenation, and the development of a dehydrogenation catalyst with strong hydrogen release capability and less loss is one of the main difficulties in the development of the organic liquid hydrogen storage technology.
CN109701588A discloses a dehydrogenation catalyst and a preparation method thereof, wherein the carrier is subjected to nitride treatment, one end of an organic matter is linked with a molecular sieve, and the other end is combined with an active metal salt to obtain a nitrogen-containing carrier catalyst, so that the defects of low activity, poor stability and easy coking of the dehydrogenation catalyst are overcome. However, it requires a nitride treatment of the carrier, and the preparation cost is high.
Therefore, there is a need to develop new dehydrogenation catalysts with active components supported on carriers.
Disclosure of Invention
The invention aims to solve the problems of high active component load, low dispersity, poor stability and large particle size of a dehydrogenation catalyst in the prior art, low dehydrogenation efficiency, high raw material decomposition rate and easy coking when the dehydrogenation catalyst is used for dehydrogenation, and provides a dehydrogenation catalyst and a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a dehydrogenation catalyst, wherein the dehydrogenation catalyst comprises: a carboxylate ion-containing carrier and an active component; the carrier containing carboxylate ions is obtained by acid hydrolysis of a carrier containing cyano groups, and the active component comprises at least one selected from VIII group elements.
In a second aspect, the present invention provides a method for preparing a dehydrogenation catalyst, wherein the method comprises the steps of:
1) Mixing a carrier containing cyano groups with acid liquor and performing first drying to obtain a carrier containing carboxyl groups;
2) And carrying out reflux, secondary drying and reduction on the active component precursor loaded on the carrier containing the carboxyl to obtain the dehydrogenation catalyst.
In a third aspect, the present invention provides a dehydrogenation catalyst prepared by the above-described preparation method.
In a fourth aspect, the present invention provides the use of the dehydrogenation catalyst described above in the dehydrogenation of the organic hydrogen storage materials dodecylhydrogen ethylcarbazole, 18H-dibenzyltoluene, methylcyclohexane and naphthalene.
Through the technical scheme, the dehydrogenation catalyst provided by the invention, and the preparation method and application thereof have the following beneficial effects:
(1) The dehydrogenation catalyst provided by the invention comprises a carrier containing carboxylate ions and an active component, wherein the carrier containing carboxylate ions is obtained by acid hydrolysis of a carrier containing cyano groups, and the carrier containing carboxylate ions is coordinated and combined with the active component, so that the active component of the dehydrogenation catalyst has low loading capacity, high dispersity, good stability and small particle size;
(2) The preparation method of the dehydrogenation catalyst provided by the invention simplifies the operation conditions and the process flow, and is convenient for industrial production;
(3) The dehydrogenation catalyst provided by the invention is used for dehydrogenation of organic hydrogen storage materials such as dodecyl hydrogen ethyl carbazole, 18H-dibenzyl toluene, methylcyclohexane and naphthalene, and can effectively improve dehydrogenation efficiency, reduce raw material decomposition rate and prevent coking.
Drawings
FIG. 1 is a TEM image of a dehydrogenation catalyst prepared according to example 1 of the present invention;
FIG. 2 XRD patterns of dehydrogenation catalysts prepared in example 1 and comparative example 1 of the present invention.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides a dehydrogenation catalyst, wherein the dehydrogenation catalyst comprises: a carboxylate ion-containing carrier and an active component; the carrier containing carboxylate ions is obtained by acid hydrolysis of a carrier containing cyano groups, and the active component comprises at least one selected from VIII group elements.
In the invention, the carrier containing carboxylate ions and the active component are coordinated and combined, so that the active component can be better anchored and dispersed on the carrier, and the dehydrogenation catalyst has the advantages of low active component loading capacity, high dispersity, good stability, small particle size and excellent catalytic effect.
According to the invention, the dehydrogenation catalyst has a specific surface area of from 80 to 270m 2 /g。
In the present invention, when the specific surface area of the catalyst is less than 80m 2 G, its micro-pores are small, its active dehydrogenation activity is reduced; the specific surface area of the catalyst is more than 270m 2 And/g, the binding force between the active component and the carrier is too weak, and the dehydrogenation activity is reduced due to the fact that the active component is easy to fall off.
According to the present invention, the cyano group-containing carrier is selected from at least one of polyarylether nitrile, polyarylether ether nitrile, L-caprolaconitrile, 4-n-propoxyphthalonitrile and malononitrile.
According to the invention, the relative density of the polyarylether nitrile is 1.1-1.4.
In the invention, the relative density of the poly (arylene ether nitrile) refers to the density ratio of the poly (arylene ether nitrile) to the air as a reference substance, and when the relative density of the poly (arylene ether nitrile) is less than 1.1, the catalyst powder particles are larger, the specific surface area is smaller, and the catalytic effect is reduced; when the relative density is more than 1.4, the catalyst powder particles of the catalyst are smaller, the specific surface area is larger, the catalyst is easy to agglomerate, and the catalytic effect is reduced.
According to the invention, the active component is selected from at least one of the platinum group metal elements, preferably palladium and/or platinum.
According to the invention, the carboxylate ion-containing support is 95 to 99.9wt% and the active component is 0.1 to 5wt% based on the total weight of the dehydrogenation catalyst.
In the present invention, when the contents of the carrier and the active component do not satisfy the above-defined ranges, the catalytic effect of the catalyst is unstable.
According to the invention, the carboxylate ion-containing carrier has a carboxylate ion content of 2 to 5wt%.
In the present invention, when the content of carboxylate ions does not satisfy the above-defined range, the catalytic effect of the catalyst is unstable.
In a second aspect, the present invention provides a method for preparing a dehydrogenation catalyst, wherein the method comprises the steps of:
1) Mixing a carrier containing cyano groups with acid liquor and performing first drying to obtain a carrier containing carboxyl groups;
2) And carrying out reflux, secondary drying and reduction on the active component precursor loaded on the carrier containing the carboxyl to obtain the dehydrogenation catalyst.
According to the invention, in step 1), the acid solution has a concentration of 40-60wt%.
According to the invention, in step 1), the mixing conditions include: stirring at 20-80deg.C for 2-12 hr.
According to the present invention, in step 1), the first drying conditions include: the temperature is 80-120 ℃ and the time is 3-6h.
According to the invention, in step 1), the mass-volume ratio of the cyano-containing carrier to the acid solution is 1g: (1-4) mL.
According to the present invention, the acid contained in the acid solution is at least one selected from the group consisting of concentrated sulfuric acid, concentrated hydrochloric acid and phosphoric acid.
According to the invention, in step 2), the mass ratio of the carrier containing carboxyl to the active component precursor is 1:0.001-0.05.
According to the invention, the active ingredient precursor is selected from PdCl 2 、Pd(NO 3 ) 2 、H 2 PtCl 6 And Pd (acac) 2 At least one of them.
According to the invention, in step 2), the process of reflow comprises: condensing and refluxing for 2-12h at normal temperature.
According to the present invention, in step 2), the second drying conditions include: the temperature is 80-120 ℃ and the time is 3-6h.
According to the invention, in step 2), the process of reduction comprises: soaking the catalyst intermediate in 15-25wt% concentration reductant solution at 20-70 deg.c for 2-4 hr, and drying at 20-70 deg.c for 6-12 hr for reduction.
In the invention, the mass ratio of the catalyst intermediate to the reducing agent is 1:3-5.
According to the invention, the reducing agent is at least one of sodium borohydride, ethylene glycol and L-ascorbic acid.
In a third aspect, the present invention provides a dehydrogenation catalyst prepared by the above-described preparation method.
In a fourth aspect, the present invention provides the use of the dehydrogenation catalyst described above in the dehydrogenation of the organic hydrogen storage materials dodecylhydrogen ethylcarbazole, 18H-dibenzyltoluene, methylcyclohexane and naphthalene.
In the present invention, organic hydrogen storage materials include, but are not limited to, dodecylhydrogen ethylcarbazole, 18H-dibenzylmethylbenzene, methylcyclohexane, and naphthalene.
In the present invention, the raw material decomposition rate means loss of a substance as a hydrogen storage carrier during the cyclic dehydrogenation.
The present invention will be described in detail by examples. In the following examples of the present invention,
the specific surface area of the dehydrogenation catalyst is measured by the BET method;
the active component load of the dehydrogenation catalyst is measured by an inductively coupled plasma mass spectrometer;
the formula for calculating dehydrogenation efficiency:
x is the selectivity of each substance measured by chromatography;
the decomposition rate of the raw materials is measured by an Shimadzu gas chromatograph;
the raw materials used in the examples and comparative examples are all commercially available.
Example 1
1) Stirring poly (arylene ether nitrile) with relative density of 1.3 and 45 weight percent of concentrated sulfuric acid for 5 hours at 40 ℃, and drying for 4 hours at 90 ℃ to obtain a carrier containing carboxyl, wherein the mass-volume ratio of the poly (arylene ether nitrile) to the concentrated sulfuric acid is 1 g/1 mL;
2) 5mg of PdCl 2 Dissolving in 0.5mL of hydrochloric acid, adding 1g of a mixture of a carrier containing carboxyl and 3mL of deionized water, stirring, condensing and refluxing for 5h at normal temperature, drying for 4h at 90 ℃, soaking the catalyst intermediate for 2.5h at 40 ℃ with 5g of sodium borohydride solution with the solubility of 18wt%, and drying for 8h at 40 ℃ for reduction to obtain a dehydrogenation catalyst A1.
FIG. 1A TEM image of a dehydrogenation catalyst prepared in example 1 of the present invention, it can be seen from FIG. 1 that the dehydrogenation catalyst has a high dispersion degree of an active component and a small particle diameter.
FIG. 2 XRD patterns of dehydrogenation catalysts prepared in example 1 of the present invention, as can be seen from FIG. 2, the comparative example 1 catalyst exhibited a PdO diffraction peak centered at 33.8 °, which indicates that larger PdO particles were formed in the support channels, whereas no diffraction peak of any Pd species was observed in example 1, due to lower Pd loading or better anchoring of Pd by the introduction of-COOH on the support surface 2+ The dispersity is improved.
Example 2
1) Stirring poly (arylene ether nitrile) with relative density of 1.1 and 55wt% of concentrated sulfuric acid for 9h at 60 ℃, and drying for 5h at 110 ℃ to obtain a carrier containing carboxyl, wherein the mass-volume ratio of poly (arylene ether nitrile) to the concentrated sulfuric acid is 1 g/2 mL;
2) 5mg of Pd (NO) 3 ) 2 Dissolving in 0.5mL of hydrochloric acid, adding 1g of a mixture of a carrier containing carboxyl and 3mL of deionized water, stirring, condensing and refluxing for 10h at normal temperature, drying for 5h at 110 ℃, soaking the catalyst intermediate for 3.5h at 50 ℃ with 5g of L-ascorbic acid solution with the solubility of 22wt%, and drying for 10h at 50 ℃ for reduction to obtain a dehydrogenation catalyst A2.
Example 3
1) Stirring poly (arylene ether nitrile) with relative density of 1.2 and 40wt% of concentrated sulfuric acid for 2h at 20 ℃, and drying for 3h at 80 ℃ to obtain a carrier containing carboxyl, wherein the mass-volume ratio of poly (arylene ether nitrile) to the concentrated sulfuric acid is 1 g/3 mL;
2) 5mg of H 2 PtCl 6 Dissolving in 0.5mL of hydrochloric acid, adding 1g of a mixture of a carrier containing carboxyl and 3mL of deionized water, stirring, condensing and refluxing for 2h at normal temperature, drying for 3h at 80 ℃, soaking the catalyst intermediate for 2h at 20 ℃ with 5g of ethylene glycol solution with the solubility of 15wt%, and drying for 6h at 20 ℃ for reduction to obtain a dehydrogenation catalyst A3.
Example 4
1) Stirring poly (arylene ether nitrile) with relative density of 1.4 and 60wt% of concentrated sulfuric acid at 80 ℃ for 12 hours, and drying at 120 ℃ for 6 hours to obtain a carrier containing carboxyl, wherein the mass-volume ratio of poly (arylene ether nitrile) to the concentrated sulfuric acid is 1g:4mL;
2) 5mg of PdCl 2 Dissolving in 0.5mL of hydrochloric acid, adding 1g of a mixture of a carrier containing carboxyl and 3mL of deionized water, stirring, condensing and refluxing for 12h at normal temperature, drying for 6h at 120 ℃, soaking the catalyst intermediate for 4h at 70 ℃ with 5g of sodium borohydride solution with the solubility of 25wt%, and drying for 12h at 70 ℃ for reduction to obtain a dehydrogenation catalyst A4.
Example 5
A dehydrogenation catalyst was prepared as in example 1, except that: and replacing the poly (arylene ether nitrile) with poly (arylene ether nitrile) to obtain the dehydrogenation catalyst A5.
Example 6
A dehydrogenation catalyst was prepared as in example 1, except that: and replacing the polyarylether nitrile with L-caprolaconitrile to prepare the dehydrogenation catalyst A6.
Example 7
A dehydrogenation catalyst was prepared as in example 1, except that: the polyether nitrile is replaced by malononitrile to prepare the dehydrogenation catalyst A7.
Example 8
A dehydrogenation catalyst was prepared as in example 1, except that: and replacing the polyarylether nitrile with 4-n-propoxyphthalonitrile to prepare the dehydrogenation catalyst A8.
Example 9
A dehydrogenation catalyst was prepared as in example 1, except that: 5mg of PdCl 2 Changed to 8mg of PdCl 2 Dehydrogenation catalyst A9 was prepared.
Example 10
A dehydrogenation catalyst was prepared as in example 1, except that: 5mg of PdCl 2 Changed to 16mg of PdCl 2 Dehydrogenation catalyst a10 was prepared.
Example 11
A dehydrogenation catalyst was prepared as in example 1, except that: 5mg of PdCl 2 Changed to 48mg of PdCl 2 Dehydrogenation catalyst a11 was prepared.
Example 12
A dehydrogenation catalyst was prepared as in example 1, except that: 5mg of PdCl 2 Change to 80mg PdCl 2 Dehydrogenation catalyst a12 was prepared.
Comparative example 1
5mg of PdCl 2 Dissolving in 0.5mL hydrochloric acid, adding into a mixture of 1g of poly (arylene ether nitrile) and 3mL of deionized water, stirring, condensing and refluxing for 5 hours at normal temperature, drying for 4 hours at 90 ℃, soaking the catalyst intermediate for 2.5 hours at 40 ℃ with 1mL of reducing agent solution with the solubility of 18%, and drying for 8 hours at 40 ℃ to obtain the dehydrogenation catalyst D1.
Comparative example 2
80mg of PdCl are added 2 Dissolving in 0.5mL hydrochloric acid, adding into a mixture of 1g of poly (arylene ether nitrile) and 3mL of deionized water, stirring, condensing and refluxing for 5 hours at normal temperature, drying for 4 hours at 90 ℃, soaking the catalyst intermediate for 2.5 hours at 40 ℃ with 1mL of reducing agent solution with the solubility of 18%, and drying for 8 hours at 40 ℃ to obtain the dehydrogenation catalyst D2.
Comparative example 3
5mg of PdCl 2 Dissolving in 0.5mL hydrochloric acid, adding into a mixture of 1g silica gel and 3mL deionized water, stirring, condensing and refluxing at normal temperature for 5h, drying at 90 ℃ for 4h, soaking the catalyst intermediate in 1mL reducing agent solution with the solubility of 18% at 40 ℃ for 2.5h, and drying at 40 ℃ for 8h to obtain the dehydrogenation catalyst D3.
Comparative example 4
80mg of PdCl are added 2 Dissolving in 0.5ml hydrochloric acid, adding into a mixture of 1g silica gel and 3ml deionized water, stirring, condensing and refluxing at normal temperature for 5 hr, drying at 90deg.C for 4 hr, and dissolving at 40deg.C with 1% solvent of 18%The catalyst intermediate was soaked in mL of the reducing agent solution for 2.5 hours and dried at 40℃for 8 hours to give dehydrogenation catalyst D4.
Test example 1
The dehydrogenation catalysts (A1-A12 and D1-D4) prepared in examples 1-12 and comparative examples 1-4 were subjected to catalytic performance tests.
The evaluation conditions were as follows: 1g of the catalyst was charged into the three-necked flask reactor, the reaction pressure was normal pressure and the temperature was 200℃and dodecylhydrogen ethylcarbazole was used as a representative raw material for hydrogen storage in an organic liquid. The results are shown in Table 1.
To examine the stability of the catalyst, X8 was defined as the conversion of the catalyst at 8h of reaction. The results are shown in Table 1.
TABLE 1
As can be seen from Table 1, examples 1 to 12 contain a dehydrogenation catalyst as compared with comparative examples 1 to 4
High dehydrogenation efficiency and low raw material decomposition rate.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (24)
1. A dehydrogenation catalyst, wherein the dehydrogenation catalyst comprises: a carboxylate ion-containing carrier and an active component; the carrier containing carboxylate ions is obtained by acid hydrolysis of a carrier containing cyano groups, and the active component comprises at least one selected from VIII group elements.
2. The dehydrogenation catalyst of claim 1, wherein the dehydrogenation catalyst has a specific surface area of from 80 to 270m 2 /g。
3. The dehydrogenation catalyst of claim 1, wherein the cyano-containing support is selected from at least one of polyaryl ether nitriles, L-caprolaconitrile, 4-n-propoxyphthalonitrile, and malononitrile.
4. A dehydrogenation catalyst according to claim 3, characterized in that the relative density of the polyarylethernitrile is 1.1-1.4.
5. The dehydrogenation catalyst of claim 1, wherein the active component is selected from at least one of the platinum group metal elements.
6. The dehydrogenation catalyst of claim 5, wherein the active component is selected from palladium and/or platinum.
7. The dehydrogenation catalyst of claim 1, wherein the carboxylate ion-containing support is from 95 to 99.9wt% and the active component is from 0.1 to 5wt%, based on the total weight of the dehydrogenation catalyst.
8. The dehydrogenation catalyst of claim 7, wherein the carboxylate ion-containing support comprises 2 to 5wt% carboxylate ion.
9. A process for preparing a dehydrogenation catalyst, wherein the process comprises the steps of:
1) Mixing a carrier containing cyano groups with acid liquor and performing first drying to obtain a carrier containing carboxyl groups;
2) And carrying out reflux, secondary drying and reduction on the active component precursor loaded on the carrier containing the carboxyl to obtain the dehydrogenation catalyst.
10. The method according to claim 9, wherein in step 1), the cyano-containing carrier is at least one selected from the group consisting of polyaryl ether nitrile, L-caprolaconitrile, 4-n-propoxyphthalonitrile and malononitrile.
11. The method of claim 10, wherein the poly (arylene ether nitrile) has a relative density of 1.1 to 1.4.
12. The method according to claim 9, wherein in step 1), the acid concentration in the acid solution is 40 to 60wt%.
13. The method of claim 9, wherein in step 1), the mixing conditions include: stirring at 20-80deg.C for 2-12 hr.
14. The method of claim 9, wherein in step 1), the first drying conditions include: the temperature is 80-120 ℃ and the time is 3-6h.
15. The method according to claim 9, wherein in step 1), the mass-to-volume ratio of the cyano-containing carrier to the acid solution is 1g: (1-4) mL.
16. The method according to claim 15, wherein the acid contained in the acid solution is at least one selected from the group consisting of concentrated sulfuric acid, concentrated hydrochloric acid and phosphoric acid.
17. The preparation method according to claim 9, wherein in step 2), the mass ratio of the carboxyl group-containing carrier to the active component precursor is 1:0.001-0.05.
18. The method of claim 17, wherein the active component precursor is selected from PdCl 2 、Pd(NO 3 ) 2 、H 2 PtCl 6 And Pd (acac) 2 At least one of them.
19. The method according to claim 9, wherein in step 2), the process of refluxing comprises: condensing and refluxing for 2-12h at normal temperature.
20. The method of claim 9, wherein in step 2), the second drying conditions include: the temperature is 80-120 ℃ and the time is 3-6h.
21. The method according to claim 9, wherein in step 2), the reducing comprises: soaking the catalyst intermediate in 15-25wt% concentration reductant solution at 20-70 deg.c for 2-4 hr, and further drying at 20-70 deg.c for 6-12 hr.
22. The method of claim 21, wherein the reducing agent is at least one of sodium borohydride, ethylene glycol, and L-ascorbic acid.
23. A dehydrogenation catalyst prepared by the preparation method of any one of claims 9-22.
24. Use of a dehydrogenation catalyst according to any one of claims 1-8 and 23 in the dehydrogenation of the organic hydrogen storage materials dodecylhydrogen ethylcarbazole, 18H-dibenzyltoluene, methylcyclohexane and naphthalene.
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